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We employed two compelling and distinct methods, Fourier Transform Infrared Spectroscopy (FTIR) and Ramped Pyrolysis Oxidation (Ramped PyrOx), to examine the quality of organic matter (OM) stored in four peatlands located along a latitudinal gradient (Tropical (4˚N), Subtropical (27˚N), Boreal (48˚N), and Polar (68˚N)). FTIR was used to quantify the relative abundance of carbohydrates, a relatively labile compound class, and aromatics, which are more recalcitrant, in a sample set of four peat cores. These samples were then prepared using Ramped PyrOx, a second, independent method of determining OM quality that mimics the natural diagenetic maturation of OM that would take place over long timescales. Previous large-scale studies using FTIR to evaluate OM quality have observed that it generally increases with increasing latitude (more carbohydrates, less aromatics). Here, we demonstrate that the Ramped PyrOx approach both validates and complements the FTIR approach. The data stemming from each Ramped PyrOx preparation was input to a model that generates an estimated probability density function of the activation energy (E) required to break the C bonds in the sample. We separated these functions into three fractions (“lowE,” “mediumE,” and “highE”) to create Ramped PyrOx variables that could be quantitatively compared to the compound class abundance data from FTIR. In assessing the agreement between the two methods, we found three significant relationships between Ramped PyrOx and FTIR variables. LowEfractions and carbohydrate content were positively correlated (R²= 0.51) while lowEfractions were negatively correlated with aromatic content (R²= 0.58). MediumEfractions were found to be positively correlated with aromatics (R²= 0.69). 

Abstract The Amazon River mobilizes organic carbon across one of the world's largest terrestrial carbon reservoirs. Quantifying the sources of particulate organic carbon (POC) to this flux is typically challenging in large systems such as the Amazon River due to hydrodynamic sorting of sediments. Here, we analyze the composition of POC collected from multiple total suspended sediment (TSS) profiles in the mainstem at Óbidos, and surface samples from the Madeira, Solimões and Tapajós Rivers. As hypothesized, TSS and POC concentrations in the mainstem increased with depth and fit well to Rouse models for sediment sorting by grain size. Coupling these profiles with Acoustic Doppler Current Profiler discharge data, we estimate a large decrease in POC flux (from 540 to 370 kg per second) between the rising and falling stages of the Amazon River mainstem. The C/N ratio and stable and radiocarbon signatures of bulk POC are less variable within the cross‐section at Óbidos and suggest that riverine POC in the Amazon River is predominantly soil‐derived. However, smaller shifts in these compositional metrics with depth, including leaf waxn‐alkanes and fatty acids, are consistent with the perspective that deeper and larger particles carry fresher, less degraded organic matter sources (i.e., vegetation debris) through the mainstem. Overall, our cross‐sectional surveys at Óbidos highlight the importance of depth‐specific sampling for estimating riverine export fluxes. At the same time, they imply that this approach to sampling is perhaps less essential with respect to characterizing the composition of POC sources exported by the river. 

ABSTRACT This study describes a procedural blank assessment of the ultraviolet photochemical oxidation (UV oxidation) method that is used to measure carbon isotopes of dissolved organic carbon (DOC) at the National Ocean Sciences Accelerator Mass Spectrometry Facility (NOSAMS). A retrospective compilation of Fm and δ 13 C results for secondary standards (OX-II, glycine) between 2009 and 2018 indicated that a revised blank correction was required to bring results in line with accepted values. The application of a best-fit mass-balance correction yielded a procedural blank of 22.0 ± 6.0 µg C with Fm of 0.30 ± 0.20 and δ 13 C of –32.0 ± 3.0‰ for this period, which was notably higher and more variable than previously reported. Changes to the procedure, specifically elimination of higher organic carbon reagents and improved sample and reactor handling, reduced the blank to 11.0 ± 2.75 µg C, with Fm of 0.14 ± 0.10 and δ 13 C of –31.0 ± 5.5‰. A thorough determination of the entire sample processing blank is required to ensure accurate isotopic compositions of seawater DOC using the UV oxidation method. Additional efforts are needed to further reduce the procedural blank so that smaller DOC samples can be analyzed, and to increase sample throughput. 

ABSTRACT In practice, obtaining radiocarbon ( 14 C) composition of organic matter (OM) in sediments requires first removing inorganic carbon (IC) by acid-treatment. Two common treatments are acid rinsing and fumigation. Resulting 14 C content obtained by different methods can differ, but underlying causes of these differences remain elusive. To assess the influence of different acid-treatments on 14 C content of sedimentary OM, we examine the variability in 14 C content for a range of marine and river sediments. By comparing results for unacidified and acidified sediments [HCl rinsing (Rinse HCl ) and HCl fumigation (Fume HCl )], we demonstrate that the two acid-treatments can affect 14 C content differentially. Our findings suggest that, for low-carbonate samples, Rinse HCl affects the Fm values due to loss of young labile organic carbon (OC). Fume HCl makes the Fm values for labile OC decrease, leaving the residual OC older. High-carbonate samples can lose relatively old organic components during Rinse HCl , causing the Fm values of remaining OC to increase. Fume HCl can remove thermally labile, usually young, OC and reduce the Fm values. We suggest three factors should be taken into account when using acid to remove carbonate from sediments: IC abundance, proportions of labile and refractory OC, and environmental matrix.